Agents for dyeing of human hair with nonionic direct dyes

ABSTRACT

A PROCESS FOR THE APPLICATION OF AGENTS WHICH IMPROVE THE DYEING OF HAIR, PARTICULARLY LIVING HUMAN HAIR, WITH NONIONIC DIRECT DYES IS DISCLOSED. THE HAIR IS TREATED WITH SOLUTIONS, DISPERSIONS OR EMULSIONS OF THE FOLLOWING COMPOUNDS: (A) CARBONIC ACID OR SULFUROUS ACID ESTERS OF ALKYLENE GLYCOLS HAVING 2 TO 4 CARBON ATOMS; (B) ESTERS OF ALIPHATIC ALCOHOLS HAVING 1 TO 8 CARBON ATOMS WITH SATURATED DICARBOXYLIC ACIDS HAVING 2 TO 8 CARBON ATOMS AND WITH AROMATIC CARBOXYLIC ACIDS; (C) PYRIDINE DERIVATIVES; (D) DITHIOHYDANTOIN, TETRAHYDROTHIOPHENE DIOXIDE; AND MIXTURES THEREOF.

Patented Feb. 23, 1971 3,565,571 AGENTS FOR DYEING OF HUMAN HAIR WITH NONIONIC DIRECT DYES Giinter Reese, Dusseldorf, Peter Berth, Dusseldorf-Benrath, and Karl-Josef Boosen, Dusseldorf-Holthausen, Germany, assignors to Therachemie Chemisch Therapeutische Gesellschaft m.b.H., Dusseldorf, Germany No Drawing. Filed Aug. 25, 1965, Ser. No. 482,582 Claims priority, application Germany, Sept. 2, 1964,

26,922 Int. Cl. A61k 7/12 US. Cl. 810.1 4 Claims ABSTRACT OF THE DISCLOSURE A process for the application of agents which improve the dyeing of hair, particularly living human hair, with nonionic direct dyes is disclosed. The hair is treated with solutions, dispersions or emulsions of the following compounds:

(a) carbonic acid or sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms;

(b) esters of aliphatic alcohols having 1 to 8 carbon atoms with saturated dicarboxylic acids having 2 to 8 carbon atoms and with aromatic carboxylic acids;

(c) pyridine derivatives;

((1) dithiohydantoin, tetrahydrothiophene dioxide; and

mixtures thereof.

The invention relates to boosters for nonionic direct dyestuifs which facilitate the dyeing of hair, more particularly human hair, and to a process for their application.

For the dyeing of hair so-called oxidation dyes are employed at a large scale, such as aromatic diamines, aminophenols or polyhydroxy compounds. However, direct dyes also have been used which have the advantage not to require the addition of oxidizers upon application. It is known from the textile industry that dyeing and the qualities of the coloring obtained thereby can frequently be improved by means of particularly high or low pH values, elevated temperatures or extension of the time of application. Upon dyeing of hair, and particularly living human hair, such methods evidently cannot be employed. Moreover, it often is necessary to apply entirely new dyes as agents for dyeing of human hair, and this is especially true for direct dyes.

It also has been attempted to improve the usefulness especially of such dyes of limited solubility, by the addition of materials as butanol, benzyl alcohol or addition products of phenols or alcohols on ethylene oxide. However, it has been found that success has been limited to very few instances.

It is the object of the invention to present agents and a process for their application which facilitate ready dyeing of hair, particularly living human hair, with nonionic direct dyestuffs, i.e., to improve the quality of the color, its intensity and resistance to rubbing and abrasion. All this is attained, according to the invention, by treating the hair with solutions, dispersions or emulsions of compounds of the following series:

(a) carbonic acid or sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms;

(b) esters of lower aliphatic alcohols having 1 to 8 carbon atoms with saturated dicarboxylic acids having 2 to 8 carbon atoms and of aromatic carboxylic acids;

(c) pyridine derivatives;

(d) dithiohydantoin or tetrahydrothiophene dioxide.

Treatment of the hair can be carried out by rinsing them with a solution or emulsion containing one or more of the compounds named above, followed by dyeing with the direct dyes in the conventional manner. However, it is equally feasible to wash the hair first and to add the agents to the last rinse directly. The concentration of the agents ranges from 0.1 to 10 weight percent, preferably 1 to 5 percent. The temperatures are 15 to 40 C., preferably room temperature.

If desired, this treatment furthermore can be combined with the actual dyeing by incorporating the compounds named in the dyeing preparation, either during the production of the latter or else shortly before its application to the hair. Concentrations and temperatures are the same as named above.

The advantages of this novel process are found in the fact that frequently the quantity of dyestuff to be applied can materially be reduced without sacrificing the intensity of the dye. It also is feasible in many instances to increase the color intensity considerably with the process according to the invention when initially a rather weak coloration is present.

A further advantage is the increase in the resistance to abrasion and rubbing with simultaneous improvement of the dyeing process.

The single effects depend, to a certain extent, on the booster used and on the characteristics of the dyestuif itself, but it has been established that the improvements named have been attained in all instances. For practical application, the compounds named below are particularly interesting from a technological and economical point of view. They are special representatives of (a)(c) above, but are not presented to be a limitation:

(a) ethylene glycol carbonate, l,3-butylene glycol carbonate and especially ethylene glycol sulfite and 1,2- propylene glycol sulfite;

(b) diethyl oxalate, ethyl benzoate, diethylphthalate;

(c) pyridine-2-carbinol, picoline carboxylic acid-N-oxide, especially 3-pyridyl hydroxymethane sulfonic acid, dipicolinic acid, picolinic acid, isonicotinic acid thioamide, picolinic acid thioamide, piperidine, pyridine-2- thiocarbinol.

If desired, mixtures of these compounds can be used, especially mixtures of compounds of the same group. It goes without saying that the mutual chemical compatibility and that with other possible present materials must be considered.

The pH value of the solutions containing these boosters can be adapted to a large measure to the prevailing requirements and desires. Good results have been obtained with preparing solutions and/or last rinses which were not alkaline, but acid or neutral.

Suitable nonionic direct dyes are especially those based upon anthraquinoneor aminoanthraquinone derivatives or azo dyes. Particularly those dyes can be employed which have been named in British Pat. 957,119 and those which are known as Celliton (registered trademark).

The dyestuffs are applied in the conventional concentrations of 0.1 to 5 weight percent, preferably 0.5 to 3 percent. If, however, the effect of increased color intensity is not desired, the commonly employed quantities can greatly be decreased, in some instances down to approximately the usual amount, with the process according to the invention.

The hair dyes can be mixed with any desired wetting agents, detergents or washing agents, especially anionic or nonionic agents. Particularly to be named are alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid ethanolamides, ethylene oxide additives on fatty acids and fatty alcohols.

Furthermore, thickeners can be added, such as methylcellulose, starch, higher fatty alcohols, Vaseline, parafiin oil and fatty acids; also perfumes, i.e., essential oils, or

3 hair grooming agents such as pantothenic acid and cholesterol.

These additives are incorporated in the commonly used quantities. As wetting agent or detergent amounts of 0.530 weight percent, as thickeners 0.l25 weight percent, are preferred, calculated on the total composition. The concentration of the dyes, depending upon the purpose, amounts to up to weight percent, preferably however, 0.1 to 2 weight percent, calculated on the total composition.

The invention now will be further illustrated by the following examples. However, it should be understood that these are given merely by way of explanation, and not of limitation, and that numerous changes may be made in the details without departing from the spirit and scope of the invention as hereinafter claimed.

EXAMPLE 1 For dyeing of naturally greyed living human hair, the same was treated for minutes at room temperature with a solution containing 1 weight percent dyestuff. The solution is adjusted to a pH of 9.5. The nonionic direct dye used was a compound having Formula 1:

II o After completed treatment, the hair had a Weakly pink color.

The color was intensified to a considerable extent when, prior to otherwise the same treatment, the hair was rinsed for 5 minutes with an aqueous solution containing 3 weight percent pyridine-Z-thiocarbinol. The intensification manifested itself by imparting to the hair a brilliant red-purple color.

EXAMPLE 2 Naturally greyed living human hair was washed with a conventional shampoo and rinsed. The last rinse water contained 5 weight percent pyridine-2-thiocarbinol. The hair then was dyed with a coloring cream having as a nonionic dye, in a concentration of 1 weight percent, a compound of the Formula 2:

The pH of this cream was 9.5, the time of application 20 minutes at room temperature. A strong red color was obtained whose intensity was considerably stronger than had been obtained with the omission of the additive to the last rinse, at otherwise like procedure.

EXAMPLE 3 4 EXAMPLE 4 For the dyeing of naturally greyed hair, a grey strand thereof was dipped into an aqueous dispersion containing 1 weight percent of a dye having Formula 3:

EXAMPLE 5 Grey hair attained a burgundy red color with a bluish cast by allowing an aqueous dispersion to act thereon consisting of 0.5 weight percent 1,4-diamino-2-(1',4',7- trioxanonyl)-anthraquinone, 4 weight percent ethylene glycol sulfite and 95.5 weight percent ammonia solution of a pH of 9.5.

By equal treatment but under omission of the glycol sulfite, the intensity of the color was much Weaker. However, in lieu of the ethylene glycol sulfite, 1,2-propylene glycol sulfite could be used with equal result.

EXAMPLE 6 Aqueous solutions or dispersions were prepared containing as dyestulf 1,4-diamino-2-chloro-3-(l,4',7'-trioxanonyl)-anthraquinone and, as further additive 5 weight percent of one of the compounds named in Table 1. The solutions or dispersions were adjusted to a pH of 9.5 with aqueous ammonia.

Grey hair was treated with these solutions for 20 minutes at room temperature, rinsed with water and then shampooed.

In all instances a considerable improvement was obtained over the same treatment with like compounds which did not contain the materials named in Table 1. This improvement consisted in a strong boost over the pink color obtained without the additives.

In lieu of the dyestutf named above, Indanthrene Red GG, Color Index 71130 can be used with equally good results.

TABLE 1 No; Material 1 Diethyl oxalate. 2 Ethyl benzoate. 3 Diethyl phthalate. 4 Ethylene glycol sulfite. 5 1,2-propylene glycol sulfite. 6 Ethylene glycol carbonate. 7 1,3-butylene glycol carbonate. 8 3-pyridylhydroxymethane sulfonic acid. 9 Z-pyridylhydroxymethane sulfonic acid. 10 Dipicolinic acid. 11 Picolinic acid. 12 Isonicotinic acid thioamide. l3 Picolinic acid thioamide. 14 Pyridine-Z-carbinol. 15 Pyridine-Z-thiocarbinol. 16 Picoline carboxylic acid-N-oxide. 17 Piperidine. 18 Dithiohydantoin. 19 Tetrahydrothiophene dioxide.

What is claimed is:

1. A process for boosting the action of a nonionic direct dye on human hair which comprises treating said hair with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.1 to 10 weight percent of compounds selected from the group consisting of (a) carbonic acid and sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms;

(b) esters of aliphatic alcohols having 1 to 8 carbon atoms with saturated dicarboxylic acids having 2 to 8 carbon atoms and with benzene and phthalic carboxylic acids;

(c) 3-pyridylhydroxymethane sulfonic acid, Z-pyridylhydroxymethane sulfonic acid, dipicolinic acid, picolinic acid, isonicotinic acid thioamide, picolinic acid thioarnde, pyridine-2-carbinol, pyridine-Z-thiocarbin01, picoline carboxylic acid-N-oxide, piperidine, pyridine-2-carboxylic acid-N-oxide mixtures thereof.

(d) dithiohydantoin, tetrahydrothiophene dioxide; and mixtures thereof; and thereafter applying said dye.

2. A process according to claim 1 wherein said compound is diethyl oxalate, ethyl benzoate, diethyl phthalate, ethylene glycol sulfite, 1,2-propylene glycol sulfite, ethylene glycol carbonate, 1,3-butylene glycol carbonate, 3-pyridylhydroxymethane sulfonic acid, 2-pyridylhydroxymethane sulfonic acid, dipicolinic acid, picolinic acid, isonicotinic acid thioamide, picolinic acid thioamide, pyridine-Z-carbinol, pyridine-Z-thiocarbinol, picoline carboxylic acid-N-oxide, piperidine, pyridine-2-carboxylic acid- N-oxide, dithiohydantoin, tetrahydrothiophene dioxide, or mixtures thereof.

3. A process for boosting the action of a nonionic direct dye on human hair which comprises treating said hair with the application of said dye in a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially to 40 C., said liquids containing substantially 0.1 to 10 weight percent of compounds selected from the group consisting of (a) carbonic acid and sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms;

(b) esters of aliphatic alcohols having 1 to 8 carbon atoms with saturated dicarboxylic acids having 2 to 8 carbon atoms and with benzene and phthalic carboxylic acids;

(c) B-pyridylhydroxymethane sulfonic acid, 2-pyridylhydroxymethane sulfonic acid, dipicolinic acid, picolinic acid, isonicotinic acid thioamide, picolinic acid thioamide, pyridine-2-carbinol, pyridine-2-thiocarbinol, picoline carboxylic acid-tN-oxide, piperidine, pyridine-Z-carboxylic acid-N-oxide, mixtures thereof;

(d) dithiohydantoin, tetrahydrothiophene dioxide, and

mixtures thereof.

4. A process according to claim 3 wherein said compound is diethyl oxalate, ethyl benzoate, diethyl phthalate, ethylene glycol sulfite, 1,2-propylene glycol sulfite, ethylene glycol carbonate, 1,3-butylene glycol carbonate, 3- pyridylhydroxymethane sulfonic acid, Z-pyridylhydroxymethane sulfonic acid, dipicolinic acid, picolinic acid, isonicotinic acid thioamide, picolinic acid thioamide, pyridine-Z-carbinol, pyridine-Z-thiocarbinol, picoline carboxylic acid-N-oxide, piperidine, pyridine-Z-carboxylic acid- N-oxide, dithiohydantoin, tetrahydrothiophene dioxide, or mixtures thereof.

References Cited UNITED STATES PATENTS 2,069,215 2/1937 Chambers 8-85X ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 

